Electronic and surface properties of Ga-doped In 2 O 3 ceramics

A. Regoutz, R. G. Egdell, D. J. Morgan, R. G. Palgrave, H. Téllez, S. J. Skinner, D. J. Payne, G. W. Watson, D. O. Scanlon

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Abstract

The limit of solubility of Ga 2 O 3 in the cubic bixbyite In 2 O 3 phase was established by X-ray diffraction and Raman spectroscopy to correspond to replacement of around 6% of In cations by Ga for samples prepared at 1250 °C. Density functional theory calculations suggest that Ga substitution should lead to widening of the bulk bandgap, as expected from the much larger gap of Ga 2 O 3 as compared to In 2 O 3 . However both diffuse reflectance spectroscopy and valence band X-ray photoemission reveal an apparent narrowing of the gap with Ga doping. It is tentatively concluded that this anomaly arises from introduction of Ga + surface lone pair states at the top of the valence band and structure at the top of the valence band in Ga-segregated samples is assigned to these lone pair states. In addition photoemission reveals a broadening of the valence band edge. Core X-ray photoemission spectra and low energy ion scattering spectroscopy both reveal pronounced segregation of Ga to the ceramic surface, which may be linked to both relief of strain in the bulk and the preferential occupation of surface sites by lone pair cations. Surprisingly Ga segregation is not accompanied by the development of chemically shifted structure in Ga 2p core XPS associated with Ga + . However experiments on ion bombarded Ga 2 O 3 , where a shoulder at the top edge of the valence band spectra provide a clear signature of Ga + at the surface, show that the chemical shift between Ga + and Ga 3+ is too small to be resolved in Ga 2p core level spectra. Thus the failure to observe chemically shifted structure associated with Ga + is not inconsistent with the proposal that band gap narrowing is associated with lone pair states at surfaces and interfaces.

Original languageEnglish
Pages (from-to)970-982
Number of pages13
JournalApplied Surface Science
Volume349
DOIs
Publication statusPublished - Sep 15 2015

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Valence bands
Electronic properties
surface properties
Surface properties
ceramics
Photoemission
valence
electronics
photoelectric emission
Cations
Energy gap
Positive ions
Spectroscopy
Ions
X rays
Core levels
spectroscopy
Chemical shift
cations
x rays

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Condensed Matter Physics
  • Physics and Astronomy(all)
  • Surfaces and Interfaces
  • Surfaces, Coatings and Films

Cite this

Regoutz, A., Egdell, R. G., Morgan, D. J., Palgrave, R. G., Téllez, H., Skinner, S. J., ... Scanlon, D. O. (2015). Electronic and surface properties of Ga-doped In 2 O 3 ceramics Applied Surface Science, 349, 970-982. https://doi.org/10.1016/j.apsusc.2015.04.106

Electronic and surface properties of Ga-doped In 2 O 3 ceramics . / Regoutz, A.; Egdell, R. G.; Morgan, D. J.; Palgrave, R. G.; Téllez, H.; Skinner, S. J.; Payne, D. J.; Watson, G. W.; Scanlon, D. O.

In: Applied Surface Science, Vol. 349, 15.09.2015, p. 970-982.

Research output: Contribution to journalArticle

Regoutz, A, Egdell, RG, Morgan, DJ, Palgrave, RG, Téllez, H, Skinner, SJ, Payne, DJ, Watson, GW & Scanlon, DO 2015, ' Electronic and surface properties of Ga-doped In 2 O 3 ceramics ', Applied Surface Science, vol. 349, pp. 970-982. https://doi.org/10.1016/j.apsusc.2015.04.106
Regoutz A, Egdell RG, Morgan DJ, Palgrave RG, Téllez H, Skinner SJ et al. Electronic and surface properties of Ga-doped In 2 O 3 ceramics Applied Surface Science. 2015 Sep 15;349:970-982. https://doi.org/10.1016/j.apsusc.2015.04.106
Regoutz, A. ; Egdell, R. G. ; Morgan, D. J. ; Palgrave, R. G. ; Téllez, H. ; Skinner, S. J. ; Payne, D. J. ; Watson, G. W. ; Scanlon, D. O. / Electronic and surface properties of Ga-doped In 2 O 3 ceramics In: Applied Surface Science. 2015 ; Vol. 349. pp. 970-982.
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